Silicon carbide crystal and method of manufacturing silicon carbide crystal

ABSTRACT

An SiC crystal ( 10 ) has Fe concentration not higher than 0.1 ppm and Al concentration not higher than 100 ppm. A method of manufacturing an SiC crystal includes the following steps. SiC powders for polishing are prepared as a first source material ( 17 ). A first SiC crystal ( 11 ) is grown by sublimating the first source material ( 17 ) through heating and precipitating an SiC crystal. A second source material ( 12 ) is formed by crushing the first SiC crystal ( 11 ). A second SiC crystal ( 14 ) is grown by sublimating the second source material ( 12 ) through heating and precipitating an SiC crystal. Thus, an SiC crystal and a method of manufacturing an SiC crystal capable of achieving suppressed lowering in quality can be obtained.

TITLE OF INVENTION

Silicon Carbide Crystal and Method of Manufacturing Silicon CarbideCrystal

TECHNICAL FIELD

The present invention relates to a silicon carbide crystal (SiC) and amethod of manufacturing an SiC crystal.

BACKGROUND ART

An SiC crystal has a large band gap and also has maximum breakdownelectric field and thermal conductivity higher than those of silicon(Si), and the SiC crystal has carrier mobility as high as that of Si andit is high also in electron saturation drift velocity and breakdownvoltage. Therefore, application to a semiconductor device required toachieve higher efficiency, higher breakdown voltage and larger capacityis expected.

An SiC crystal employed in such a semiconductor device is manufacturedwith a sublimation method representing a vapor phase epitaxy method, asdisclosed, for example, in Japanese Patent Laying-Open No. 2005-008473(PTL 1), Japanese Patent Laying-Open No. 2005-314217 (PTL 2), and thelike.

PTL 1 discloses lowering in nitrogen concentration in a grown SiCcrystal by using a graphite crucible of which impurity nitrogenconcentration is not higher than 50 ppm for growing an SiC crystal. PTL2 discloses a method of growing an SiC crystal by using a carbon sourcematerial having boron concentration not higher than 0.11 ppm and asilicon source material having boron concentration not higher than 0.001ppm.

CITATION LIST Patent Literature

PTL 1: Japanese Patent Laying-Open No. 2005-008473

PTL 2: Japanese Patent Laying-Open No. 2005-314217

SUMMARY OF INVENTION Technical Problem

The present inventor noted use of SiC powders for polishing (hereinafteralso referred to as GC (Green Silicon Carbide)) as a source material forgrowing an SiC crystal. This GC contains a large amount of impuritiessuch as aluminum (Al) and iron (Fe) and it is difficult to remove suchimpurities as Al and Fe from GC. Therefore, use of GC as a sourcematerial in the manufacturing method in PTL 1 above leads to highimpurity concentration in a grown SiC crystal. Meanwhile, use of a GCsource material as a source material in the manufacturing method in PTL2 above leads to high concentration of such impurities as Al and Fe in agrown SiC crystal, although boron impurity concentration is low.

When concentration of such impurities as Al and Fe in a grown SiCcrystal is high, quality lowers due to these impurities.

The present invention was made in view of the problems above, and anobject of the present invention is to provide an SiC crystal and amethod of manufacturing an SiC crystal capable of achieving suppressedlowering in quality.

Solution To Problem

An SiC crystal according to the present invention has Fe concentrationnot higher than 0.1 ppm and Al concentration not higher than 100 ppm.

The present inventor conducted dedicated studies about to which rangeconcentration of Fe and Al impurities in an SiC crystal should belowered to lessen influence on quality due to impurities. Consequently,the present inventor found that influence on quality of an SiC crystalcan be lessened by decreasing Fe and Al to the range above. Therefore,according to the SiC crystal of the present invention, an SiC crystalachieving suppressed lowering in quality can be realized.

In the SiC crystal above, preferably, micropipe density is not higherthan 10/cm². In the SiC crystal above, preferably, etch pit density isnot higher than 10000/cm².

The present inventor conducted dedicated studies in order to improvequality of an SiC crystal, and consequently, succeeded in realizing anSiC crystal in which at least one of micropipe density and etch pitdensity is in the range above. Then, the present inventor also foundthat an SiC crystal can suitably be used for a semiconductor device ifat least one of micropipe density and etch pit density is in the rangeabove. Therefore, by employing an SiC crystal in which at least one ofmicropipe density and etch pit density is in the range above, quality ofa semiconductor device can be improved.

A method of manufacturing an SiC crystal according to the presentinvention includes the following steps. SiC powders for polishing (GC)are prepared as a first source material. A first SiC crystal is grown bysublimating the first source material through heating and precipitatingan SiC crystal. A second source material is formed by crushing the firstSiC crystal. A second SiC crystal is grown by sublimating the secondsource material through heating and precipitating an SiC crystal.

The present inventor noted GC as a starting source material formanufacturing an SiC crystal and conducted dedicated studies in order toimprove quality of an SiC crystal manufactured by using GC.Consequently, the present inventor conceived that, by fabricating asecond source material by crushing a first SiC crystal grown with theuse of a first source material and growing a second SiC crystal by usingthe second source material, the second SiC crystal can contain lessimpurities such as Fe and Al than the first SiC crystal. Based on thisconception, the present invention uses as the second source material, amaterial obtained by crushing the first SiC crystal grown by using GC asthe first source material, and hence impurity concentration in thesecond SiC crystal can be lowered even though GC is used as a startingsource material. Therefore, lowering in quality due to impurities in themanufactured SiC crystal can be suppressed.

In the method of manufacturing are SiC crystal above, preferably, in thestep of forming a second source material, the second source material isformed such that a plurality of peaks of size distribution are presentin a range not smaller than 1 μm and not greater than 3 mm and 95% ormore particles are present in a range of ±50% from a center of each peakof the size distribution.

The present inventor conducted dedicated studies in order to furtherenhance quality of a grown crystal. Consequently, the present inventornoted size distribution of a second source material and completed theinvention above. By achieving a grain size of the second source materialas above, a filling factor of the second source material in a cruciblecan be improved. Therefore, the second SiC crystal can be manufacturedwith lower cost. In addition, since influence on concentration of asublimation gas of the second source material can be lowered, micropipedensity, etch pit density and the like of the second SiC crystal grownby using the second source material can effectively be lowered.Therefore, lowering in quality of a grown SiC crystal can further belessened.

In the method of manufacturing an SiC crystal above, preferably, in thestep of forming a second source material, the second source materialhaving Fe concentration not higher than 0.1 ppm and Al concentration nothigher than 100 ppm is formed.

Thus, an SiC crystal having Fe concentration not higher than 0.1 ppm andAl concentration not higher than 100 ppm can be manufactured.

In the method of manufacturing an SiC crystal above, the step of forminga second source material preferably includes the step of washing thecrushed first SiC crystal with an acid solution.

Thus, a heavy metal such as Fe in the first SiC crystal can effectivelybe removed. Therefore, impurity concentration in a manufactured SiCcrystal can further be lowered.

The method of manufacturing an SiC crystal above preferably furtherincludes the steps of forming a third source material by crushing thesecond SiC crystal and growing a third SiC crystal by sublimating thethird source material through heating and precipitating an SiC crystal.

The present inventor conceived that, by employing a material obtained bycrushing a grown crystal as a source material and growing an SiCcrystal, impurity concentration in a grown SiC crystal can be lowered.Therefore, by repeating the step of growing an SiC crystal by using amaterial obtained by crushing a grown SiC crystal as a source material,impurity concentration in a grown SiC crystal can gradually be lowered.Therefore, by repeating the step of growing an SiC crystal by using amaterial obtained by crushing a grown crystal as a source material threeor more times, lowering in quality of a manufactured SiC crystal canfurther be suppressed.

Advantageous Effects of Invention

According to the SiC crystal and the method of manufacturing an SiCcrystal of the present invention, lowering in quality due to impuritiescan be suppressed.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a perspective view schematically showing an SiC crystal in anembodiment of the present invention.

FIG. 2 is a cross-sectional view schematically showing a process formanufacturing an SiC crystal in the embodiment of the present invention.

FIG. 3 is a cross-sectional view schematically showing the process formanufacturing an SiC crystal in the embodiment of the present invention.

FIG. 4 is a diagram for illustrating size distribution of a secondsource material in the embodiment of the present invention.

FIG. 5 is a cross-sectional view schematically showing the process formanufacturing an SiC crystal in the embodiment of the present invention.

FIG. 6 is a cross-sectional view schematically showing the process formanufacturing an SiC crystal in the embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

An embodiment of the present invention will be described hereinafterwith reference to the drawings. In the drawings below, the same orcorresponding elements have the same reference characters allotted anddescription thereof will not be repeated.

FIG. 1 is a perspective view schematically showing an SiC crystal 10 inan embodiment of the present invention. Initially, SiC crystal 10 in oneembodiment of the present invention will be described with reference toFIG. 1.

As shown in FIG. 1, SiC crystal 10 is, for example, a substrate having acircular two-dimensional shape. SiC crystal 10 contains Fe atconcentration not higher than 0.1 ppm and Al at concentration not higherthan 100 ppm. Lower concentration of Fe and Al is preferred, however,from a point of view of ease of realization, Fe concentration is, forexample, not lower than 0.002 ppm and Al concentration is, for example,0.02 ppm. As concentration of Fe and Al is thus lowered, increase inmicropipe density or etch pit density can effectively be suppressed andvariation in resistivity can also effectively be suppressed.Concentration of Fe and Al is a value measured, for example, withICP-AES.

SiC crystal 10 has micropipe density preferably not higher than 10/cm²and more preferably not higher than 2/cm². Micropipe density is a valuedetermined, for example, from the number of threading hollow defectscounted in a surface etched by immersion in a potassium hydroxide (KOH)melt at 500° C. for 1 to 10 minutes, by using a Nomarski differentialinterference microscope.

SiC crystal 10 has etch pit density preferably not higher than 10000/cm²and more preferably not higher than 9300/cm². Etch pit density is avalue determined, for example, from the number of etch pits counted in asurface etched by immersion in a KOH melt at 500° C. for 1 to 10minutes, by using a Nomarski differential interference microscope.

SiC crystal 10 is preferably a single crystal. Though a polytype of SiCcrystal 10 is not particularly limited, for example, 4H—SiC ispreferred.

In succession, a method of manufacturing SiC crystal 10 in the presentembodiment will be described with reference to FIGS. 1 to 6. In thepresent embodiment, SiC crystal 10 is manufactured with a sublimationmethod. It is noted that FIGS. 2, 3, 5, and 6 are each a cross-sectionalview schematically showing a process for manufacturing an SiC crystal inthe present embodiment. FIG. 4 is a diagram for illustrating sizedistribution of a second source material in the present embodiment.

A primary construction of an SiC crystal manufacturing apparatus willinitially be described with reference to FIG. 2 and the like. Themanufacturing apparatus includes a crucible 101 and a heating portion(not shown) for heating crucible 101. The heating portion is arranged,for example, around an outer circumference of crucible 101.

In the present embodiment, crucible 101 has a lower portion for holdinga source material and an upper portion functioning as a cover of thelower portion for holding the source material. Crucible 101 is made, forexample, of graphite.

Though the manufacturing apparatus may include various elements otherthan the above, for the sake of convenience of description, illustrationand description of these elements will not be provided.

As shown in FIG. 2, SiC powders for polishing (GC) are prepared as afirst source material 17. For example, commercially available GC isemployed. Prepared first source material 17 is placed in the lowerportion of crucible 101.

Then, as shown in FIG. 3, a first SiC crystal 11 is grown by sublimationof first source material 17 through heating and precipitation from a gasof first source material 17. In growing first SiC crystal 11 by using GCas a source material, it is preferred not to arrange a seed substrate.

Specifically, first source material 17 is heated by the heating portionat a temperature at which first source material 17 sublimates. As aresult of this heating, first source material 17 sublimates and asublimation gas is generated. This sublimation gas is again solidifiedat a position opposed to the first source material in crucible 101, thatis, in the upper portion of crucible 101, that is set at a temperaturelower than first source material 17.

By way of example of a growing temperature, for example, first sourcematerial 17 is held at a temperature from 2000° C. to 3000° C., and aposition opposed to first source material 17 is held at a temperaturefrom 1900° C. to 2200° C., which is lower than a temperature of firstsource material 17. In addition, an atmospheric pressure in crucible 101is held preferably at 400 Torr or lower. Thus, first SiC crystal 11grows at a position opposed to first source material 17. First SiCcrystal 11 thus grown is, for example, polycrystalline.

By setting a temperature of first source material 17 to 2000° C. orhigher, a growth rate of first SiC crystal 11 can be increased. Bysetting a temperature of first source material 17 to 3000° C. or lower,damage of crucible 101 can be suppressed. A growing temperature may beheld at a constant temperature during growth, however, it may also bevaried at a certain rate during growth.

In addition, by setting an atmospheric pressure in crucible 101 to 400Torr or lower, a growing rate can be increased.

Then, a second source material 12 (see FIG. 5) is formed by crushingfirst SiC crystal 11. In this step, for example, the following areperformed. Specifically, the inside of crucible 101 is cooled to a roomtemperature. Then, grown first SiC crystal 11 is taken out of crucible101. This first SiC crystal 11 is crushed, for example, with a crusher.It is noted that a crushing method is not particularly limited.

In this step, as shown in FIG. 4, second source material 12 ispreferably formed such that a plurality of (in FIG. 4, three peaks A, Band C) size distribution peaks are present in a range not smaller than 1gm and not greater than 3 mm and 95% or more particles are present in arange of ±50% from respective centers A1, B1 and C1 of size distributionpeaks A, B and C. As centers A1, B1 and C1 of size distribution peaks A,B and C are not smaller than 1 gm and not greater than 3 mm and 95% ormore particles are present in the range of ±50% from respective centersA1, B1 and C1 of size distribution peaks A, B and C, a filling factor atthe time when crucible 101 is filled with second source material 12 canbe increased. Thus, a time period for growth in growing a second SiCcrystal 14 by using this second source material 12 is shortened andinfluence on concentration of a gas of second source material 12 thatsublimated during growth can be suppressed. Therefore, quality of secondSiC crystal 14 grown by using this second source material 12 can beenhanced.

From such a point of view, second source material 12 is preferablyformed such that center A1 of smallest grain size peak A is present in arange not smaller than 1 μm and not greater than 100 μm and center C1 oflargest grain size peak C is present in a range not smaller than 200 μmand not greater than 3 mm. Similarly, such second source material 12that peak A includes particles not less than 10 weight % and not morethan 50 weight %, peak C includes particles not less than 30 weight %and not more than 80 weight %, and the remainder represents other peak(in FIG. 4, peak B) is further preferably formed.

Here, the phrase above that “95% or more particles are present in arange of ±50% from respective centers A1, B1 and C1 of size distributionpeaks A, B and C” means that 95% or more of the whole particles ofsecond source material 12 is present between 150% particle sizes A2, B2and C2 with respect to particle sizes at centers A1, B1 and C1 and 50%particle sizes A3, B3 and C3 with respect to particle sizes at centersA1, B1 and C1, respectively. It is noted that the number of particlesize distribution peaks may be two, or four or more.

In addition, “size distribution” above is a value, for example,determined in conformity with JIS R6001 1998.

Though a method of forming second source material 12 having sizedistribution as above is not particularly limited, second sourcematerial 12 can be formed, for example, by crushing first SiC crystal 11and thereafter making selection so as to achieve size distribution inthe range above. It is noted that second source material 12 may beformed by crushing first SiC crystal 11 so as to have size distributionas above.

In addition, after first SiC crystal 11 is crushed, crushed first SiCcrystal 11 is preferably washed with an acid solution. Though an acidsolution is not particularly limited, aqua regia is preferably used. Byusing an acid solution, in particular aqua regia, such a heavy metal asFe attached to first SiC crystal 11 during crushing can be removed. Inaddition, washing, for example, with hydrochloric acid is furtherpreferred.

Second source material 12 formed as above preferably contains Fe atconcentration not higher than 0.1 ppm and A1 at concentration not higherthan 100 ppm. In addition, second source material 12 formed as above isplaced in the lower portion of crucible 101.

Then, as shown in FIG. 5, a seed substrate 13 is arranged in the upperportion of crucible 101 so as to be opposed to second source material 12in crucible 101. A main surface of seed substrate 13 may have a circularor quadrangular shape. Though a material for seed substrate 13 is notparticularly limited, from a point of view of enhancing quality of grownsecond SiC crystal 14, an SiC substrate is preferred and the material ismore preferably identical in grown polytype (crystal polymorphism),which means that, for example, in a case where an SiC crystal intendedto be grown is 4H—SiC, seed substrate 13 is also 4H—SiC. It is notedthat this step may be omitted.

Then, as shown in FIG. 6, second SiC crystal 14 is grown by sublimationof second source material 12 through heating and precipitation from agas of second source material 12. In the present embodiment, second SiCcrystal 14 is grown on seed substrate 13. Second SiC crystal 14 ispreferably a single crystal. Since a method of growing second SiCcrystal 14 is substantially the same as the method of growing first SiCcrystal 11, description thereof will not be repeated.

Then, the inside of crucible 101 is cooled to a room temperature. Then,an ingot including seed substrate 13 and second SiC crystal 14 is takenout of crucible 101. This ingot may be employed as SiC crystal 10 shownin FIG. 1. Namely, SiC crystal 10 in FIG. 1 may be manufactured bygrowing first SiC crystal 11 by using first source material 17, formingsecond source material 12 by crushing first SiC crystal 11, and growingsecond SiC crystal 14 by using second source material 12.

In order to further decrease impurities in SiC crystal 10, the stepabove is preferably repeated. Namely, the step of forming a third sourcematerial by crushing second SiC crystal 14 and the step of growing athird SiC crystal by sublimation of the third source material throughheating and precipitation from a gas of the third source material arepreferably further performed. The steps in this one cycle can decreaseimpurities, for example, by approximately 10%.

As the steps above are repeated, concentration of impurities in grownSiC crystal 10 is lowered, however, from a point of view ofmanufacturing an SiC crystal preferable for use in a semiconductordevice, the steps above are preferably repeated until concentration ofFe in the grown SiC crystal is not higher than 0.1 ppm and concentrationof Al therein is not higher than 100 ppm. In addition, in order toreliably fabricate such an SiC crystal, an SiC crystal is furtherpreferably manufactured by repeating the steps above until a sourcematerial having Fe concentration not higher than 0.1 ppm and Alconcentration not higher than 100 ppm can be fabricated and by growingan SiC crystal by using this source material.

By performing the steps above, an ingot including a seed substrate andan SiC crystal formed on the seed substrate can be manufactured. Thisingot may be employed as SiC crystal 10 shown in FIG. 1. Alternatively,SiC crystal 10 shown in FIG. 1 may be manufactured by removing seedsubstrate 13 from the ingot. In a case of removal, only seed substrate13 may be removed or seed substrate 13 and a part of the grown SiCcrystal may be removed.

A removal method is not particularly limited, and for example, such amechanical removal method as cutting, grinding and cleavage can beemployed. Cutting refers to mechanical removal of at least seedsubstrate 13 from an ingot, for example, by using a wire saw. Grindingrefers to grinding in a direction of thickness by bringing a grindstoneinto contact with a surface while it is rotating. Cleavage refers todivision of a crystal along a crystal lattice plane. It is noted thatsuch a chemical removal method as etching may be employed.

In a case where manufactured SiC crystal 10 has a large thickness, SiCcrystal 10 shown in FIG. 1 may be manufactured by cutting a plurality ofSiC crystal slices from the grown SiC crystal. In this case, cost formanufacturing one slice of SiC crystal 10 can be lowered.

Thereafter, one surface or opposing surfaces of an SiC crystal may beplanarized by grinding, polishing or the like, as necessary.

As described above, a method of manufacturing SiC crystal 10 in theembodiment of the present invention includes the steps of preparing SiCpowders for polishing as first source material 17, growing first SiCcrystal 11 by sublimating first source material 17 through heating andprecipitating an SiC crystal, forming second source material 12 bycrushing first SiC crystal 11, and growing second SiC crystal 14 bysublimating second source material 12 through heating and precipitatingan SiC crystal.

The present inventor conceived that, by fabricating second sourcematerial 12 by crushing first SiC crystal 11 grown with the use of firstsource material 17 and growing second SiC crystal 14 by using secondsource material 12, second SiC crystal 14 can contain impurities such asFe and Al less than first SiC crystal 11. According to the method ofmanufacturing SiC crystal 10 in the present embodiment, first SiCcrystal 11 is grown by using a GC source material as first sourcematerial 17, second source material 12 is formed by crushing this firstSiC crystal 11, and second SiC crystal 14 is grown by using secondsource material 12. Therefore, even with the use of GC high inconcentration of Fe and Al as a starting source material, second SiCcrystal 14 can be lower in impurity concentration than first SiC crystal11. Therefore, lowering in quality due to impurities in manufactured SiCcrystal 10 can be lessened.

Further, GC is readily available, which is useful in industrializedmanufacturing of SiC crystal 10. Thus, SiC crystal 10 can bemanufactured with lower cost.

According to such a method of manufacturing SiC crystal 10 in thepresent embodiment, SiC crystal 10 having Fe concentration not higherthan 0.1 ppm and Al concentration not higher than 100 ppm can bemanufactured. The present inventor conducted dedicated studies about towhich range concentration of Fe and Al impurities in SiC crystal 10should be lowered to lessen influence on quality due to theseimpurities. Consequently, the present inventor found that influence onquality of SiC crystal 10 (for example, crystal defects such asmicropipes or etch pits) can be lessened by decreasing Fe and Al to therange above. Therefore, according to SiC crystal 10 in the presentembodiment, lowering in quality can be suppressed.

EXAMPLES

In the present example, an effect of growing first SiC crystal 11 byusing GC as first source material 17, forming second source material 12by crushing first SiC crystal 11, and growing second SiC crystal 14 byusing second source material 12 was examined.

Present Inventive Example 1

In Present Inventive Example 1, an SiC crystal was manufacturedbasically in accordance with the method of manufacturing an SiC crystalin the embodiment described above.

Specifically, initially, generally commercially available GC forabrasive was prepared as first source material 17. This first sourcematerial was arranged in the lower portion of crucible 101 as shown FIG.2, while nothing was arranged in a cover of crucible 101 opposed to anoutermost surface of first source material 17.

Then, first SiC crystal 11 was grown by sublimation of first sourcematerial 17 through heating and precipitation of a gas of first sourcematerial 17. Here, a temperature of the lower portion of crucible 101,that is, first source material 17, was set to 2300° C., a temperature ofthe upper portion of crucible 101 was set to 2000° C., and a pressure incrucible 101 was set to 1 Torr. Grown first SiC crystal 11 waspolycrystalline.

Then, first SiC crystal 11 was crushed. Crushing was carried out byusing a crusher. Thereafter, crushed first SiC crystal 11 was washedwith aqua regia and further washed with hydrochloric acid. Then, secondsource material 12 was formed by using crushed first SiC crystal 11 suchthat there are three size distribution peaks A, B and C, the center ofsmallest grain size peak A was less than 1 μm, and the center of largestgrain size peak C exceeded 3 mm, as shown in FIG. 4. In addition, secondsource material 12 was formed such that 95% or more particles werepresent in the range of ±50% from the center of each size distributionpeak. Size distribution of second source material 12 was determined inconformity with JIS R6001 1998. This second source material 12 wasarranged in the lower portion in crucible 101.

Then, as shown in FIG. 5, 4 H—SiC having micropipe density of 10/cm² wasprepared as seed substrate 13. This seed substrate 13 was arranged inthe upper portion in crucible 101 to be opposed to second sourcematerial 12.

Then, second SiC crystal 14 was grown by sublimation of second sourcematerial 12 through heating and precipitation of a gas of second sourcematerial 12. The method of growing second SiC crystal 14 was the same asthe method of growing first SiC crystal 11.

By performing the steps above, an SiC crystal in Present InventiveExample 1 was manufactured. Namely, second SiC crystal 14 was adopted asthe SiC crystal in Present Inventive Example 1.

Present Inventive Example 2

A method of manufacturing an SiC crystal in Present Inventive Example 2was basically the same as in Present Inventive Example 1, however, itwas different in that second source material 12 of which center oflargest grain size peak C was not smaller than 200 μm and not greaterthan 3 mm was formed in the step of forming second source material 12.

Present Inventive Example 3

A method of manufacturing an SiC crystal in Present Inventive Example 3was basically the same as in Present Inventive Example 1, however, itwas different in that second source material 12 of which center ofsmallest grain size peak A was not smaller than 1 μm and not greaterthan 100 μm was formed in the step of forming second source material 12.

Present Inventive Example 4

A method of manufacturing an SiC crystal in Present Inventive Example 4was basically the same as in Present Inventive Example 1, however, itwas different in that second source material 12 of which center ofsmallest grain size peak A was not smaller than 1 μm and not greaterthan 100 μm and of which center of largest grain size peak C was notsmaller than 200 μm and not greater than 3 mm was formed in the step offorming second source material 12.

Comparative Example 1

A method of manufacturing an SiC crystal in Comparative Example 1 wasbasically the same as in Present Inventive Example 1, however, it wasdifferent in that the step of forming a second source material bycrushing first SiC crystal 11 was not performed. Namely, first SiCcrystal 11 was adopted as the SiC crystal in Comparative Example 1.

(Evaluation Method)

Al concentration, Fe concentration, micropipe density, and etch pitdensity of SiC crystals in Present Inventive Examples 1 to 4 andComparative Example 1 were determined as follows.

Al and Fe concentrations were determined with ICP (Inductive CoupledPlasma)-AES (Atomic Emission Spectrometry). It is noted that Aldetection limit was 0.02 ppm and Fe detection limit was 0.002 ppm.

Micropipe density (MPD) was determined based on the number of threadinghollow defects in an etched surface of an SiC crystal counted by using aNomarski differential interference microscope, after the SiC crystals inPresent Inventive Examples 1 to 4 and Comparative Example 1 were slicedto have a plane distant by 10 mm from a plane in contact with seedsubstrate 13 and immersed in a KOH melt at 500° C. for 1 to 10 minutes.In addition, micropipe density of the SiC crystal grown on seedsubstrate 13 with respect to micropipe density of seed substrate 13 (MPDof crystal/MPD of seed substrate in Table 1) was also calculated.

Etch pit density (EPD) was determined based on the number of etch pitsin an etched surface of an SiC crystal counted by using a Nomarskidifferential interference microscope, after the SiC crystals in PresentInventive Examples 1 to 4 and Comparative Example 1 were sliced to havea plane distant by 10 mm from a plane in contact with seed substrate 13and immersed in a KOH melt at 500°C for 1 to 10 minutes.

Table 1 below shows these results.

TABLE 1 Present Inventive Present Inventive Present Inventive PresentInventive Comparative Example 1 Example 2 Example 3 Example 4 Example 1Center of Grain Size A < 1 μm A < 1 μm 1 μm ≦ A ≦ 100 μm 1 μm ≦ A ≦ 100μm — 3 mm < C 200 μm ≦ C ≦ 3 mm 3 mm < C 200 μm ≦ C ≦ 3 mm (Not Crushed)Al Concentration 0.02 to 100 ppm 0.02 to 100 ppm 0.02 to 100 ppm 0.02 to100 ppm  105 ppm Fe Concentration 0.002 to 0.1 ppm 0.002 to 0.1 ppm0.002 to 0.1 ppm 0.002 to 0.1 ppm 0.15 ppm MPD of Crystal/ 85 to 95% 55to 80% 40 to 60% Less than 40% 100% or higher MPD of Seed Substrate MPDof Crystal 6 to 10/cm² 5 to 8/cm² 3 to 6/cm² 2/cm² or less 12 to 20/cm²(Count/cm²) EPD of Crystal 8000 to 9300/cm² 6500 to 7800/cm² 4800 to6000/cm² 4100 to 5200/cm² 12000 to 15000/cm² (Count/cm²)

(Evaluation Results)

As shown in Table 1, Present Inventive Examples 1 to 4 in which firstSiC crystal 11 was grown by using first source material 17, secondsource material 12 was formed by crushing first SiC crystal 11, andsecond SiC crystal 14 was grown by using second source material 12 couldbe lower in Al and Fe concentrations than Comparative Example 1. Inaddition, it was found that, as a result of such manufacturing, an SiCcrystal containing Fe at concentration not higher than 0.1 ppm and Al atconcentration not higher than 100 ppm could be realized.

In addition, it was found that the SiC crystals in Present InventiveExamples 1 to 4 could be lower in micropipe density and etch pit densitythan the SiC crystal in Comparative Example 1. Moreover, it was alsofound that takeover of micropipes in seed substrate 13 was less in theSiC crystals in Present Inventive Examples 1 to 4 than in the SiCcrystal in Comparative Example 1.

Further, it was found that Present inventive Example 4 in which thesecond source material was formed in the step of forming a second sourcematerial such that there were a plurality of size distribution peaks inthe range not smaller than 1 μm and not greater than 3 mm and 95% ormore particles were present in the range of ±50% from the center of eachsize distribution peak could be further lower in micropipe density andetch pit density than Present Inventive Examples 1 to 3. Furthermore, itwas also found that takeover of micropipes in seed substrate 13 wasfurther less.

From the foregoing, it was confirmed in the present examples thatimpurities could be decreased and lowering in quality could besuppressed by growing first SiC crystal 11 by using first sourcematerial 17, forming second source material 12 by crushing first SiCcrystal 11, and growing second SiC crystal 14 by using second sourcematerial 12.

Though the embodiment of the present invention has been described above,combination of features in the embodiment as appropriate is alsooriginally intended. It should be understood that the embodimentdisclosed herein is illustrative and non-restrictive in every respect.The scope of the present invention is defined by the terms of theclaims, rather than the embodiment described above, and is intended toinclude any modifications within the scope and meaning equivalent to theterms of the claims.

REFERENCE SIGNS LIST

10 SiC crystal; 11 first SiC crystal; 12 second source material; 13 seedsubstrate; 14 second SiC crystal; 17 first source material; 101crucible; A, B, C peak; A1, B1, C1 center; and A2, A3, B2, B3, C2, C3peak.

1-3. (canceled)
 4. A method of manufacturing a silicon carbide crystal,comprising the steps of: preparing powders of silicon carbide forpolishing as a first source material; growing a first silicon carbidecrystal by sublimating said fast source material through heating andprecipitating a silicon carbide crystal; forming a second sourcematerial by crushing said first silicon carbide crystal; and growing asecond silicon carbide crystal by sublimating said second sourcematerial through heating and precipitating a silicon carbide crystal, insaid step of forming a second source material, said second sourcematerial is formed such that a plurality of peaks of size distributionare present in a range not smaller than 1 μm and not greater than 3 mmand 95% or more particles are present in a range of ±50% from a centerof each peak of said size distribution.
 5. (canceled)
 6. The method ofmanufacturing a silicon carbide crystal according to claim 4, wherein insaid step of forming a second source material, said second sourcematerial having concentration of iron not lower than 0.002 ppm and nothigher than 0.1 ppm and concentration of aluminum not lower than 0.02ppm and not higher than 100 ppm is formed.
 7. The method ofmanufacturing a silicon carbide crystal according to claim 4, whereinsaid step of forming a second source material includes the step ofwashing crushed said first silicon carbide crystal with an acidsolution.
 8. The method of manufacturing a silicon carbide crystalaccording to claim 4, further comprising the steps of: forming a thirdsource material by crushing said second silicon carbide crystal; andgrowing a third silicon carbide crystal by sublimating said third sourcematerial through heating and precipitating a silicon carbide crystal.